A Formal Rearrangement of Allylic Silanols

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2021 Jul 2

PMID 34201779

Citations 12

Authors

Ranjeet A Dhokale

Frederick J Seidl

Shyam Sathyamoorthi

Affiliations

Soon will be listed here.

Abstract

We show that 1M aqueous HCl/THF or NaBH/DMF allows for demercurative ring-opening of cyclic organomercurial synthons into secondary silanol products bearing terminal alkenes. We had previously demonstrated that primary allylic silanols are readily transformed into cyclic organomercurials using Hg(OTf)/NaHCO in THF. Overall, this amounts to a facile two-step protocol for the rearrangement of primary allylic silanol substrates. Computational investigations suggest that this rearrangement is under thermodynamic control and that the di-tert-butylsilanol protecting group is essential for product selectivity.

Citing Articles

Fun With Unusual Functional Groups: Sulfamates, Phosphoramidates, and Di-tert-butyl Silanols.

Sathyamoorthi S European J Org Chem. 2024; 27(9).

PMID: 39309710 PMC: 11415259. DOI: 10.1002/ejoc.202301283.

Intramolecular Silanoxy-Michael Reactions with Pendant Nitroalkenes: Racemic and Enantioselective.

Joshi H, Sathyamoorthi S J Org Chem. 2024; 89(19):14197-14203.

PMID: 39305247 PMC: 11452265. DOI: 10.1021/acs.joc.4c01625.

Large Scale Epoxide Opening by a Pendant Silanol.

Thomas A, Nagamalla S, Sathyamoorthi S Organic Synth. 2024; 100:446-468.

PMID: 38274130 PMC: 10809772. DOI: 10.15227/orgsyn.100.0446.

Dancing Silanols: Stereospecific Rearrangements of Silanol Epoxides into Silanoxy-Tetrahydrofurans and Silanoxy-Tetrahydropyrans.

Joshi H, Thomas A, Mague J, Sathyamoorthi S Org Chem Front. 2023; 10(10):2556-2562.

PMID: 38037597 PMC: 10688609. DOI: 10.1039/d3qo00427a.

Ring Opening of Aziridines by Pendant Silanols Allows for Stereospecific Preparations of 1'-Amino-tetrahydrofurans.

Nirpal A, Nagamalla S, Mague J, Sathyamoorthi S J Org Chem. 2023; 88(13):9136-9156.

PMID: 37253098 PMC: 10330687. DOI: 10.1021/acs.joc.3c00763.

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